Where André Villas-Boas appeared to have given up on Salomon Kalou, Roberto Di Matteo seems to have presented the 26-year-old Ivory Coast striker with a new lease of life. Last night saw Kalou named in the starting lineup for the fourth time in the six matches since the former assistant manager took charge and he repaid the show of faith with a 75th-minute winner that offers Chelsea an excellent chance of reaching the Champions League semi-finals for the sixth time in nine years.

Kalou, preferred to Daniel Sturridge, was just one of the surprises Di Matteo had up his sleeve last night. If the first leg of a Champions League quarter-final seemed a strange occasion on which to give Paulo Ferreira his third start of the season, many would have seen it as an even odder night on which to relegate another 33-year-old to the substitutes' bench. The last time a Chelsea manager omitted Frank Lampard from the starting lineup for an away leg of a knockout match in this competition, it turned out to be one of the decisions that cost Villas-Boas his job.

Had the Portuguese manager still been in charge, it would have been tempting to assume that he had left out the England international as a disciplinary measure after hearing him make what could be construed as unhelpful comments on Chelsea's own television channel in the run-up to last night's match. "We're not as good as we used to be," Lampard had announced. While clearly justified, that assessment is the sort of thing that usually stays within the confines of the dressing room, particularly at such a tense moment in a difficult season.

Whether or not that was on the mind of Di Matteo, the decision of Chelsea's caretaker manager was a dramatic one, given the criticism that rained down on his predecessor's head following the match in Naples. The omission of Lampard on that occasion led some observers to accuse him of basic footballing illiteracy as the team lost 3-1, leaving themselves needing a miracle in the return leg – and, a few days after Di Matteo's promotion, achieving it.

Di Matteo's instinct on Tuesday night seemed to be to lean towards players with experience of Portuguese conditions. Not just Ferreira – born in Cascais, a few kilometres up the coast from Lisbon, and one of the players José Mourinho brought with him from Porto – but David Luiz and Ramires, the two Brazilians formerly with Benfica, and Raul Meireles, also once of Porto, were on duty at the start. José Bosingwa, a third ex-Porto man, was selected among the substitutes.

While the two captains, John Terry and Luisão, were tossing the coin before the kick-off, there was the extraordinary sight of Ferreira, David Luiz and Ramires running to embrace Jorge Jesus, the Lisbon club's manager. To English eyes, in the moments before the start of a game of such significance, this might have seemed a little too cosily fraternal but the outcome was to prove it meaningless.

Sightings of Ferreira have been so infrequent in recent seasons that most Chelsea fans probably have to be reminded of the Portuguese right-back's squad number. But he was into the action quickly enough, trundling across to cut out a pass from Oscar Cardozo intended for Bruno César in the second minute. A couple of minutes later, as Pablo Aimar's free-kick was knocked back across the goalmouth, Ferreira was probably fortunate that his attempt at an acrobatic clearance failed to make any sort of contact a couple of yards from his own goalline.

As Benfica continued to probe the Chelsea defence it was possible to admire the artistry of Aimar – one of the many Argentinian No10s, along with Marcelo Gallardo, Ariel Ortega and Juan Román Riquelme, to be acclaimed a "new Maradona" in the decade before the arrival of Lionel Messi. They were almost as numerous as "new Bob Dylans" in the 1970s but Aimar has survived that early notoriety and, now 32, was at the heart of most of his side's best buildups, along with the darting Nicolás Gaitán and the strong, skilful Axel Witsel. It may not have been a coincidence that Chelsea's winner came barely five minutes after he had been withdrawn.

Both sides enjoyed narrow escapes either side of the interval. The increasing intensity of Benfica's attacks during the second half, however, offered Chelsea the opportunity to profit on the break and, although the visitors had no one to match Aimar's finesse on the ball, eventually the persistence of Ramires and Torres down the right flank enabled Kalou to tuck away a goal that must have made Di Matteo feel that his gambles had all come off.

Several minutes after the final whistle had confirmed the success of Chelsea's mission, Ramires and David Luiz were the last players to leave the pitch, bathed in a warm ovation from their former fans, who had whistled ex-Porto players incessantly but now rose above their disappointment to contrive a civilised postscript to the contest.